CN105007913A - Process for making HMF from sugars with reduced byproduct formation, and improved stability HMF compositions - Google Patents
Process for making HMF from sugars with reduced byproduct formation, and improved stability HMF compositions Download PDFInfo
- Publication number
- CN105007913A CN105007913A CN201480009838.5A CN201480009838A CN105007913A CN 105007913 A CN105007913 A CN 105007913A CN 201480009838 A CN201480009838 A CN 201480009838A CN 105007913 A CN105007913 A CN 105007913A
- Authority
- CN
- China
- Prior art keywords
- hmf
- sugar
- hydroxymethylfurfural
- acid
- hexose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 150000008163 sugars Chemical class 0.000 title 1
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 150
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- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical group O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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- 238000000638 solvent extraction Methods 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
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- 239000001384 succinic acid Substances 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
- A61K31/341—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide not condensed with another ring, e.g. ranitidine, furosemide, bufetolol, muscarine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/08—Solutions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
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Abstract
Disclosed is a process for making HMF or a derivative of HMF by dehydrating one or more hexose sugars in a reduced oxygen environment. In another, related aspect, a method for improving the stability and resistance to degradation of an HMF product involves adding one or more antioxidants to the HMF product.
Description
Background technology
The present invention relate in one aspect for from sugar (and particularly but and unrestricted, from hexose carbohydrate as glucose and fructose) manufacture the method for Hydroxymethylfurfural.A second aspect, the present invention relates to the Hydroxymethylfurfural product produced by dehydration from this type of sugar.
Agricultural raw material (as starch, cellulose, sucrose or inulin) is the parent material of the cheapness for the manufacture of hexose (as glucose and fructose).These hexoses are dewatered produce except other products (as levulic acid and formic acid), HMF (is also called as Hydroxymethylfurfural (HMF).HMF and its 2,5-relevant disubstituted furan derivatives have been considered to for having very large potentiality in the field of the intermediate chemicals from regenerated resources.More specifically, different functional due to it, has advised by HMF for the production of product such as polymer, solvent, surfactant, medicine and plant protection product widely, and can having reported that HMF has antibacterial and antiseptical characteristic.HMF or a kind of key component, in the synthesis of diversified compound (as furfuryl group glycol, dialdehyde, ester, ether, halogenide and carboxylic acid) or as a kind of parent material or intermedium.The noticeable example of the compound can prepared from HMF is FDCA (or FDCA), and it can be prepared from the ether of HMF, HMF or ester derivant by oxidizing process, see, such as, the US 7 of the people such as Sanborn, 317,116 and US 2009/0156841.Discuss FDCA renewable substitute of bio-based as p-phthalic acid in the production of such as so millions of tonnes of polyester polymers of PETP or butylene terephthalate.Also the phthalic acid ester plasticiser that FDCA ester substitutes for PVC is assessed in the recent period, see such as WO2011/023491 A1 and WO 2011/023590 A1, both all transfer Ying Chuan Ai Sennuo company (Evonik Oxeno GmbH), and the people such as R.D. SANDERSON Cael (R.D.Sanderson), " journal of applied (Journal of Appl.Pol.Sci.) " 1994,53rd volume, 1785-1793 page.
In addition, HMF to be considered to for the development bio-fuel of biomass derived, fuel as a kind of continuable substitute of Fossil fuel is useful.HMF has additionally been assessed as the treatment for sicklemia.In brief, HMF is a kind of important chemical compound, and is finding the synthetic method of large-scale production HMF (there is not the impurity of significant quantity, by-product and remaining parent material) a similar century always.
Although correspondingly known that HMF can be standby by Dehydration from sugar for a long time, be at first 1895 from fructose by Dull (chemical newspaper (Chem.Ztg.), 19,216) and from sucrose by Kiermayer (chemical newspaper (Chem.Ztg.), 19,1003) preparing, there are different opinions in the precise mechanism that chemist is for many years formed from some sugar about HMF.As nearest at the people such as Weingarten " kinetics and reaction engineering (Kinetics andReaction Engineering of Levulinic Acid Production from Aqueous GlucoseSolutions) from aqueous dextrose solution production levulic acid " chemistry and sustainability, the energy and material (ChemSUSChem) 2012,5th volume, involved by 1280-1290 page (2012), " generally speaking, about from C
6there are two kinds of suggestions in the mechanism that carbohydrate forms HMF.This reaction of a kind of theory hypothesis is carried out via 1,2-enediol intermediate of acyclic.Another kind of theory considers and is forming a kind of fructofuranose base cyclic intermediate in HMF from fructose." particularly; about glucose, Weingarten reports that same to there are two kinds of HMF are the theories how to be formed from glucose: " a kind of theory propose from glucose formed HMF to carry out via fructose and compared with glucose fructose proposed close do not exist can owing to its high reactivity.On the contrary, other authors claim that glucose directly can be converted into HMF by the cyclisation of the 3-deoxidation-glucosone intermediate formed by the glucose of open loop form.In this, the low affinity that glucose to the relatively low conversion ratio of HMF is existed in this open loop form (stability due to glucopyranosyl sugar form in aqueous) by it causes.”
Although form butt formula really about the dehydration product observed by HMF and other in the dehydration of hexose carbohydrate (as fructose and glucose) correspondingly seem there is no most important consensus, but however there is a kind of consensus, no matter how mechanism may work and no matter how intermediate species can be formed by this type of mechanism, some undesired by-products always produce (no matter by the reaction relating to intermediate species or relate to HMF) together with HMF, make not yet to realize a kind of method with the economy of the extensive manufacture HMF of good yield.Complications results from the rehydrated of HMF, and this situation produces by-product, as levulic acid and formic acid.Another kind of undesired side reaction comprises the HMF of generation humin polymer and/or the polymerization of fructose, and humin polymer is solid waste product.Other complications may be selected due to solvent and produce.The water capacity is easily disposed and is dissolved fructose, but the polymer of unfortunately low selectivity and increase is formed and humin increase under aqueous conditions.
The realization of the economic commodity production of HMF also hindered by the trend of the suitable unstability of HMF and degraded, makes HMF be proved to be difficulty from the purification itself various by-product and unreacted sugar.When being exposed to for a long time at the temperature can distilling desired product, such as, HMF and the impurity relevant to synthetic mixture trend form the catabolite as tar.Due to this thermal instability, falling film vacuum distillator must be used.Even in so a kind of device, heating surface forms resinoid solid, thus cause rotor stall and dwell time frequently, make this operation inefficiency.Use distillation and added non-volatile solvents (as PEG-600) and carry out work on hand to stop the accumulation (Cope, U.S. Patent number 2,917,520) of solid humin polymer.Unfortunately, the use of Polyethylene Glycol causes the formation of HMF-PEG ether.
The rather unstable of process HMF and also other nearest effort of degraded trend have been sought or have formed more stable and segregative HMF derivant (such as, HMF ester and ether derivant) or remove HMF from being exposed in those conditions (such as acid condition, trend contributes to its degraded) rapidly.
An example of former approach can find in the US2009/0156841 of the people such as the Sanborn previously quoted, and which provides from carbohydrate sources by this carbohydrate sources to be contacted a kind of method of producing substantially pure HMF and HMF ester with solid-phase catalyst; " substantially pure " be defined as referring to about 70% or more greatly, optionally about 80% or larger or the about 90% or larger purity of HMF.
The method of producing HMF ester from carbohydrate sources and organic acid relates to and a post, heats a kind of carbohydrate parent material and an a kind of solvent in one embodiment, and makes heated carbohydrate and solvent continuously flow through a kind of solid-phase catalyst to form HMF ester under a kind of organic acid existence.This solvent is removed to provide a kind of substantially pure HMF ester by rotary evaporation.In another embodiment, a kind of carbohydrate and organic acid are heated in the solution to form a kind of HMF ester together with solid catalyst.Then can by produced HMF ester by filtering, evaporate, extract and distilling or its any combination purification.
An example of the latter's method can find in the WO 2009/012445 of the people such as Dignan, wherein propose HMF to manufacture in the following manner, the aqueous solution of mixing or stirring fructose and inorganic acid catalyst and the immiscible organic solvent of a kind of water, to form a kind of emulsion of aqueous phase and organic facies, then heats this emulsion at an elevated pressure and allows this aqueous phase and organic facies to be separated in a flow through reactors.HMF is present in aqueous phase and organic facies with about equal amount, and such as by vacuum evaporation and vacuum distilling from organic facies and by making aqueous phase remove from both through ion exchange resin.Residual fructose and aqueous phase keep together.For initial aqueous phase, support that high fructose level is to use solvent relatively in a small amount relative to the amount of reacted fructose.
In the WO 2013/106136 authorizing the people such as Sanborn, we describe a kind of for manufacturing HMF or HMF derivant (such as from aqueous hexose sugar juice, ester or ether derivant) new method, wherein according to some embodiment, by aqueous hexose solution being quickly heated up to reaction temperature from surrounding and carried out acid catalyzed dehydration by being cooled fast by the unconverted sugar mixture of this HMF and/or HMF derivant before being separated the residual sugar product being ready to ferment from HMF and/or HMF derivative products.In addition, be preferably limited in when aqueous hexose solution has been introduced into reactor and HMF and/or HMF ether products begin to cool down between time.
By accepting the restricted conversion per pass to HMF, the HMF's formed from any given aqueous hexose solution is restricted to the whole exposure temperature conditions that is acid, that raise, and preferably produces considerably less to not having undesired or disabled by-product as humin (requiring refuse process).Separation and the recovery of these products are simplified, and HMF and become known for suppressing to be reduced to a degree by the level of other hexose dehydration products of fermentative production of ethanol in residual sugar product, thus these residual sugar products can be directly used in alcohol fermentation if desired.As described and the feature of the method for carrying out is very high sugared accountability (accountabilities) and high transformation efficiency, wherein low-down sugar loss is obvious.
Summary of the invention
Following present simplification of the present invention general introduction to provide the basic comprehension of some in its aspect.This general introduction is not summary widely of the present invention and it is neither intended to determine that key of the present invention or epochmaking element are not intended to describe its scope yet.This sole purpose summarized is that the prelude using a kind of form of simplification as the more detailed description presented after a while presents concepts more of the present invention.
In this case, in one aspect, the present invention relates to a kind of still diverse ways of some solved in these difficulties, these difficulties especially manufacture in commercial-scale HMF in searching and run into from from corn wet milling or dry grinding or the common hexose sugar from the cellulosic sections of lignocellulose biomass, such as, by providing, one or more hexose sugar are passed through in the method subtracting in oxygen environment the derivant manufacturing HMF or HMF of dewatering.
At another related aspect, the present invention relates to and a kind ofly improve the stability of HMF product and the method for degradation resistance by being combined with one or more antioxidants by HMF product, this HMF product is as produced from the acid dehydration of one or more hexose sugar, wherein " antioxidant " is interpreted as broadly referring to those compounds of complicated phenomenon and the combination of compound of the organic oxidation (comprising autoxidation) in the natural or synthesis source directly or indirectly can limiting or even prevent (model of action regardless of concrete) monomer or polymer property, and relate to the HMF compositions of the improvement stability comprising one or more antioxidants itself further.Therefore, such as, as used herein " antioxidant " will be interpreted as those materials itself that comprise and be described to antioxidant routinely and be described routinely or the material of different classification, such as oxygen scavenger.
Going back in another, the present invention relates to a kind of HMF product stability before using for improvement of storage and the method for degradation resistance, this HMF product is as produced from the acid of one or more hexose sugar dehydration, and the method is included in one and subtracts in oxygen environment and store this HMF product.
Brief Description Of Drawings
Fig. 1 is the schematic diagram according to the inventive method in an illustrative examples.
The detailed description of illustrative examples
The rather unstable of HMF and the trend of degraded are indicated.Known HMF is exposed to acidity, degraded that the temperature conditions of rising contributes to HMF, but the present invention is the discovery also playing a kind of unapprehended effect up to now based on the oxidation (especially comprising autoxidation) of HMF.By a kind of subtract the dehydration of carrying out one or more hexose sugar in oxygen environment and or by HMF is combined with one or more antioxidants, the stability of this HMF and the remarkable improvement of degradation resistance can be realized.
Although those skilled in the art are as allowed it to use any known actual utilization of method of derivant making one or more hexoses dewater to form HMF or form HMF as desired by easily understanding character of the present invention, but only for purposes of illustration, schematically show the embodiment 10 of the inventive method in FIG.Particularly, embodiment 10 relates in addition according to the method for a kind of amendment of the WO 2013/106136 of the people such as above-mentioned Sanborn, wherein this dehydration to be carried out and/or wherein one or more antioxidants are combined with HMF and/or the HMF derivant manufactured according to following methods a kind of subtracting in oxygen environment, the method as the carrying out described in this application or as describe wherein but dehydration subtracted in oxygen environment in one carry out.
Forward Fig. 1 to now, dehydrated so that the aqueous hexose overall solution manufacturing HMF or HMF derivant can comprise one or more hexoses (hexose).In the particular embodiment, this aqueous hexose solution can comprise one or both more common hexose glucoses and fructose and will comprise glucose and fructose in certain embodiments.The embodiment 10 schematically shown in FIG is based on a kind of aqueous hexose solution comprising glucose and fructose.
In this process 10, as the glucose of acid or enzyme hydrolysis or cellulosic material hydrolysis can be used first in step 12 by being converted into a kind of mixture with the glucose of aqueous hexose sugar juice 14 form and fructose with using a kind of isomerase enzymatic derived from starch.For being well-known from starch manufacture glucose and the method for a part for glucose being converted into fructose, such as, in the manufacture of high-fructose corn syrup.Alternately, certainly, derived from sucrose or Radix Betae instead of isomerized fructose derived from glucose can be combined with desired ratio with glucose.In still another embodiment of the invention, the isomerization of glucose can be used to add, and blended combination from the fructose in other known sources is to be provided for the combination of the glucose and fructose that form aqueous hexose sugar juice for further processing.Expediently, this aqueous hexose sugar juice 14 can be equivalent to a kind of current high-fructose corn syrup product, such as, HFCS 42 (comprising about 42% fructose and about 53% glucose), HFCS90 (is obtained by additional purification by HFCS 42, about 90% fructose and separately about 5% grape sugar and maltose) or HFCS 55 (comprise about 55% fructose, usually obtained by blended HFCS 42 and HFCS90), make current HFCS production capacity may be used for manufacturing HMF and derivative products to return to improve assets utilization and to improve capital, as HFCS demand and price and HMF and HMF derivant demand and price instruction.
Then this aqueous hexose sugar juice 14 stands acid catalyzed dehydration in step 16 to provide the mixture 18 of HMF and unconverted sugar.Because fructose is more prone to dehydration than glucose, higher by than in hexose sugar juice 14 of the ratio of glucose in the mixture 18 of unconverted sugar.The composition of the mode that HMF and the unconverted hexose relative quantity of sugar in mixture 18 and glucose and the relative quantity of fructose in unconverted sugar moieties can be carried out according to sour dehydration 16 and aqueous hexose sugar juice 14 and changing.In general, certainly, when HMF produces more favourable than the alcohol production of unconverted residual sugar, consider that identical sour dehydration conditions HFCS 90 will produce more HMF than HFCS 55, and HFCS 55 will produce more (being dehydrated into HMF because fructose is easier than glucose) than HFCS 42.
In certain embodiments, as mentioned above, by this aqueous hexose sugar juice 14 being quickly heated up to desired dehydration temperature from room temperature and then carrying out this acid catalyzed dehydration 16 by making the unconverted sugar mixture of this HMF/ 18 cool fast before get out the residual sugar product fermented from HMF product separation.Equally, also limit from introducing sugar juice 14 until time of beginning to cool down of the unconverted sugar mixture of HMF/.
By this way by accepting the restricted conversion per pass to HMF, the HMF formed is correspondingly restricted to the whole exposure under temperature conditions that is acid, that raise, makes preferably to produce considerably less to not having undesired or disabled by-product as humin (needing refuse process).Separation and the recovery of these products are simplified, and HMF and become known for suppressing to be reduced to a degree by the level of other hexose dehydration products of fermentative production of ethanol in residual sugar product, thus these residual sugar products can be directly used in alcohol fermentation if desired.
Therefore, typically this mixture 18 will comprise the HMF from 10% to 55% molar yield, the unconverted residual sugar from 30% to 80% molar yield and be not more than the other materials (as furfural, levulic acid, humin etc.) of 10% molar yield.Preferably, this mixture 18 will comprise the HMF from 30% to 55% productive rate, the unconverted residual sugar from 40% to 70% productive rate and be not more than the other materials (as furfural, levulic acid, humin etc.) of 5% productive rate.More preferably, this mixture 18 will comprise the HMF from 45% to 55% productive rate, the unconverted residual sugar from 25% to 40% productive rate and be not more than the other materials (as furfural, levulic acid, humin etc.) of 5% productive rate.
Except seeking the HMF of restriction formation to the whole exposure under temperature conditions that is acid, that raise, in the illustrative examples 10 of dewatering according to the present invention, subtract in oxygen environment in one and carry out this acid-catalyzed dehydration step 16, the content wherein lower than aerial oxygen is dominant.This oxygen is preferably replaced by a kind of noble gas (such as, nitrogen or argon).Preferably, to introduce before this aqueous hexose sugar juice 14 or at least this aqueous hexose sugar juice 14 to a kind of acid catalyst for carrying out this dehydration 16 any exposure before, in this space reactor, set up one subtract oxygen environment.
Get back to Fig. 1 now, then the HMF in mixture 18 is separated by absorption, solvent extraction or these combination in separating step 20 with unconverted residual sugar, with produce a kind of HMF product stream or part 22 and a kind of be ready to ferment sugar stream or part 24, this sugar stream or partly can optionally be supplied to an alcohol fermentation step 26 for the production of a kind of ethanol product 28.
Absorption in step 20 can by any material preferentially adsorbing HMF in this mixture 18 from the hexose sugar of remnants.Have been found that very effective material is on the HMF retaining formation in this acid-catalyzed dehydration step 16 and any levulic acid
v-493 macropore styrene-divinylbenzene resin (CAS 69011-14-9, Dow Chemical (the The Dow Chemical Company of available, Midland, MI), this resin is described as having by its manufacturer the bulk density that the particle diameter of 20-50 sieve mesh, the average pore size of 46 dusts and the pore volume of 1.16mL/g, the surface area of 1100 square metres/g and 680g/ rise.Washing with alcohol is effective for the HMF that desorption major part has been adsorbed, and uses this resin of washing with acetone to provide the quantitative recovery of adsorbed HMF subsequently.A kind of substitute is AMBERLITE
tMxAD
tM-4 polystyrene divinylbenzene polymeric adsorbent resin (CAS 37380-42-0, philadelphia, pa Rhom and Hass (Rohm & Haas Company, Philadelphia, PA)), there is the resin of non-functionalized of pore volume of 1.08g/mL dry density, the surface area of 725 meters squared per gram, the average pore size of 50 dusts, the wet mesh size of 20-60 and 0.98mL/ gram.Other be applicable to adsorbents can be active carbon, zeolite, aluminium oxide, clay, non-functionalized resin (
aF-5,
s7968,
vPOC1064 resin, all from Lanxess Corporation (Lanxess AG)),
polystyrene divinylbenzene fluoropolymer resin (the CAS 37380-42-0 of XAD-4 macro porous crosslinking, philadelphia, pa Rhom and Hass) and cation exchange resin, see US 7,317,116 (Sanborn) and US afterwards 7,897,794 (Geier and Soper).Desorption solvent can comprise polar organic solvent, such as, and alcohol (as ethanol, amylalcohol, butanols and isoamyl alcohol) and ethyl acetate, methyltetrahydrofuran and oxolane.
Methyl ethyl ketone and especially ethyl acetate is comprised, because the latter is to HMF affinity, the low boiling point (77 DEG C) very large with levulic acid and be easily separated from water for solvent-extracted applicable solvent.As what prove in some example of applying at WO 2013/106136, can be completed by a series of extraction into ethyl acetate and almost reclaim sugar and HMF completely from mixture 18.Additionally, although the sugar of the remnants reclaimed by other means is still suitable for being directly machined as a solid entity into ethanol in alcohol fermentation step 26 subsequently, those recovery after observing use ethyl acetate quantified extract are even significantly less the suppression under the condition of non-optimal.Other solvents multiple have been suggested or for synthesize with HMF and HMF derivant and in document that recovery in binary system is relevant, and these can suitably in context of the present invention.The example of other useful solvents is butanols, isoamyl alcohol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diethyl ether, cyclopenta dimethyl ether, methyltetrahydrofuran and methyl butyl ether.
Alcohol fermentation step 26 can comprise any known process, thus can be one or more products (at least to a certain extent by fermentation means) comprising ethanol by the hexose sugar feedstock conversion of the type represented by the sugar stream being ready to ferment or part 24.Because contemplated that aerobic and anaerobic processes, it uses multiple yeast (such as, Kluyveromyces lactis, separate fat Kluyveromyces sp, saccharomyces cerevisiae, Saccharomyces uvarum, rub and receive yeast, saccharomyces pastorianus, saccharomyces bayanus, saccharomyces ellipsoideus (s.ellipsoidues), shehatae candida, candida melibiosica, candida intermedia) in any one or various bacteria (such as, clostridium sporogenes, clostridium indolis, clostridium sphenoides, Soxhlet clostridium, Ba Kaxi candida mycoderma (candida bracarensis), candida dubliniensis, zymomonas mobilis, bottle spiral shell belong to fermentation single cell bacterium) in any one, these yeast or antibacterial have the ability of producing ethanol under aerobic or anaerobic condition and other suitable conditions from the sugar stream being ready to ferment or part 24.Other details of the fermentation of the concrete yeast (or antibacterial) used and the yeast (or antibacterial) using these different are by the conventional select permeability of the technical staff in fermentation arts, although the following examples prove function of a kind of common anaerobism yeast strain (saccharomyces cerevisiae).In view of sugar stream or part 24 are derived from a kind of method for the manufacture of sour dehydration product HMF, can preferably following yeast or antibacterial, its be proved to be particularly with by acid hydrolysis of biomass and/or the cellulosic sections that carrys out authigenic material derived from lignocellulose biomass sugar together with use.Such as, aerobe Corynebacterium glutamicum R is in the people such as Sakai " inhibitor that lignocellulose derives is to the effect of hypertrophy length and by stoping the Corynebacterium glutamicum R of growth to produce ethanol (Effect ofLignocellulose-Derived Inhibitors on Growth of and Ethanol Production byGrowth-Arrested Corynebacterium glutamicum R) ", application and environmental organism (Applied and Environmental Biology), 73rd volume, 7th phase, 2349-2353 page is evaluated as the organic acid for the dilute acid pretreatment carrying out authigenic material in (in April, 2007), a kind of replacement scheme of the removing toxic substances measure of furan and phenol by-product, and find it is likely.
Although HMF (and/or HMF ether, determine as the case may be) and the amount of unconverted residual sugar can change a little, preferably obtain highly sugared accountability in all of the embodiments illustrated, wherein " sugared accountability " be interpreted as referring to be can identify in mixture 18 molar yield of product add and (substantially HMF (and/or HMF ether), levulic acid, furfural and remaining unconverted sugar molar yield add and) inputing to the percentage ratio that can occupy in the sugar in this sour dehydration 16.Preferably, be at least 70%, more preferably at least 80% according to the feature of the process 10 of amendment of the present invention and most preferably at least 90% total sugar accountability.
The sugar stream being ready to ferment or part 24 can also be used for whole or in part other objects outside alcohol production.Such as, the sugar in stream or part 24 can be recycled to the beginning of the sour dehydration 16 for the production of additional HMF or HMF ether.Can also be hydrogenated as sugar alcohol is for the production of other biological base fuel and fuel additive (be different from or except ethanol) by the hexose sugar flowed or part 24 represents, see, such as, the US 7,678,950 of the people such as Yao.Can by the sugar in stream or part 24 according to the fermentation of known method with produce lysine or lactic acid or for the manufacture of another kind of dehydration product as levulic acid.Consider the feature of sugar stream or the part 24 provided by described method, also other application will be obvious for those skilled in the art.
Be referred to the purposes of some expections of HMF product stream or part 22, but an important consideration application will be use a kind of type (Mid-Century type) Co/Mn/Br oxidation catalyst manufacture in Middle Ages 2 under oxidative conditions, in 5-furandicarboxylic acid (FDCA), as (submitted on August 28th, 2012 at the U.S. Patent Application Publication No. US 2009/1056841 of the people such as Sanborn and patent cooperation treaty application serial number PCT/US12/52641, for " for the production of bio-based succinic acid and 2, method (the Process for Producing Both BiobasedSuccinic Acid and 2 of both 5-furandicarboxylic acids, 5-Furandicarboxylic Acid) ", be disclosed as WO2013/033081 now) middle description.In use oxygen source can be exposed in this HMF product stream or part 22 are indirectly for conversion process or in addition, make HMF (or the HMF derivant that degraded is responsive, although to less degree) undesirable degraded when being predictable by autoxidation (oxidation for carrying out HMF product stream or part 22 or its part to relate to the example of the autotelic interactional conversion process of oxygen and HMF with the method for producing such as FDCA), preferably combine by one or more oxidants and this HMF product stream or part 22 or with its part (can be exposed to predicting in a kind of oxygen source and be in the risk of degraded by autoxidation).
Although following instance utilizes butylated hydroxyanisol (BHA) as anti-oxidant additives, it will be appreciated by those skilled in the art that many materials are well-known and are used as antioxidant or are used as oxygen scavenger under the background of other purposes, and select except BHA may be used for the material (or combination of material) in method of the present invention and the amount required for this type of material of the stability and degradation resistance that determine improving HMF or the HMF derivant of otherwise easily being degraded by autoxidation is fully in the ability of those skilled in the art.Consider for the great interest in FDCA and the FDCA ester of different polymer applications, as previously mentioned, previously had been found that those materials expectations being suitable as very much antioxidant in polymer composition obtained commercial wider purposes in the practice of the invention.This type of material various such as can be, Munich, Germany Han Zeer publishing house (Carl Hanser Verlag, Munich, Germany), plastic additive handbook (thePlastics Additive Handbook), 1st chapter of the 5th edition, finds during name is called " antioxidant (Antioxidants) " (2001).
As previously shown, preferably sour dehydration 16 was exposed to acidity with the conversion per pass of a kind of HMF of being limited to and by formed HMF, the mode of temperature conditions of rising carries out.The hexose sugar juice 14 cooled fast by hexose sugar juice 14 Fast Heating and by the unconverted sugar mixture of HMF/ produced by this sour dehydration 16 for specified rate realizes those objects to make us wishing.In addition, once aqueous hexose solution 14 has reached desired range of reaction temperature, the degree of temperature conditions that this aqueous hexose solution keeps standing this acidity, rising has preferably also been limited.Although optimal conditions will change from an embodiment a little to next embodiment, such as, contrasting HFCS 55 at processing HFCS 42 contrasts in HFCS 90, be shown clearly in applying at WO ' 708, in general, for the quality based on the hexose sugar in sugar juice 14 by weight about 0.5% concentrated sulphuric acid content (or for other acid catalysts, the acid strength of equivalence), from the reaction temperature of 175 DEG C to 205 DEG C, in the solid body load capacity from the sugar in 10% to 50% scope, from the final solid bulk concentration of 10% to 25%, and from the averaged residence of 2 to 10 minutes or the response time seemingly favourable." averaged residence or response time " or similar term refer to from sugar juice 14 being introduced into a reactor until begin to cool down mixture 18 elapsed time as used herein.
Generally speaking, certainly, it will be preferred that processing has compared with the hexose sugar of heavy load amount instead of the sugar juice 14 of less load capacity, although with regard to whole sugared accountability and observe in other respects some coordinate (trade-off), and these by needs consider when determining for given charging the optimum condition observed.Similarly, relatively mild reaction condition generally provides less conversion ratio, but the sugared accountability of enable increase.
For the instantiation of 40% dry solid supported HFCS 42 charging providing the final solid bulk concentration being up to 20%, use the shorter response time and the temperature to higher-end seemingly preferred, such as, at 200 DEG C 5 minutes.For HFCS 90, in view of identical sour initial concentration, reaction temperature can from the scope of 185 DEG C to 205 DEG C, the solid body load capacity of the hexose sugar in sugar juice 14 can from 30% to 50% and provide 8% to 15% final solid bulk concentration, and the response time can from 5 to 10 minutes.
As the explanation contrasting the consideration involved by another kind of charging in a kind of charging of processing, for HFCS 90 compared to HFCS 42, cannot process the final solid bulk concentration of 20% by identical whole sugared accountability, and lower final solid bulk concentration is indicated as preferably.For the final solid bulk concentration of 10%, observe the reaction temperature of 185 DEG C and the response time of 10 minutes provides favourable result.It should be pointed out that for can be different from those conditions considered for the sugar of the fresh supply in sugar juice 14 in the condition flowed or in part 24, the sugar of recovery is favourable, wherein recirculation is considered for the other HMF product of manufacture.
Under any circumstance, the heating to desired reaction temperature preferably completes being no more than in 15 minutes, preferably completes in less 11 minutes, more preferably being no more than in 8 minutes, and still more preferably completes being no more than in 5 minutes.Example as applied for by WO 2013/106136 shows, compared with charging more fast, in a certain amount of environment hexose sugar juice quick feeding to the aqueous acid matter of heat (in two minutes) give HMF selectivity, productive rate and whole sugared accountability one or more on consistent improvement, even consider the hexose sugar juice of this amount introduce completely with between beginning to cool down through the identical time.From reaction temperature to 50 DEG C and lower quick cooling preferably being no more than 5 minutes, especially interior realization in 3 minutes or less.
More specifically, compare with wherein this sugar juice 14 and acid catalyst being added in a reactor and being then heated to desired reaction temperature together step by step, one combine sugar juice 14 and close to or be in the acid catalyst in the thermal reactor of desired reaction temperature batch reactor in provide the result of improvement.
About continuity method, a kind of applicable means for this sugar juice 14 of Fast Heating and this acid catalyst will be that live (open) steam injects.Live (open) steam injection device on a kind of commercially available line, from the hydro-thermal company (Hydro-ThermalCorporation of Wisconsin State Wo Jixiao 400 pilot law court, 400 Pilot Court, Waukesha, WI) Hydro-ThermalHydroheater
tM, sonic flow is injected in the thin layer of liquid (as sugar juice 14) and flows through a series of gap from an inlet tube.Accurately vapor stream is adjusted to a degree by a variable-area nozzle, thus require exit fluid temperature large liquid regulate than interior be controlled in 0.5 degrees Fahrenheit.In the connecting pipe of a particular design, turbulent mixture occurs, wherein adjustable shear rate is in response to passing the vapor stream of this series of gaps and the adjustment (or the pressure drop striden across) of liquid stream.The equipment of this generic features such as at US 5,622,655; US 5,842,497; US 6,082,712; And US 7,152, describe in 851.
In the example of this kind equipment of use reported in WO 2013/106136, an individual system is comprised from the highest HMF yield of HFCS42 syrup and sugared accountability, this system: sulphuric acid (wt 0.5% by sugar), (wherein 1.48MPa gauge pressure is to the system back pressure of 1.52MPa gauge pressure (215-220 pound/square inch) for the initial solid bulk concentration of 20% and the Fast Heating of reactant mixture injected by live (open) steam, the steam pressure of 1.9MPa gauge pressure (275 pounds/square inch), the time of under the reaction temperature provided 5-6 minute is being provided by live (open) steam) and the quick cooling of product mixtures before earth pressure release.Reaction controlling set point as monitored by temperature control component is 200 DEG C and is 166 DEG C at the maximum temperature that the end of stationary tube realizes.Obtain the HMF being up to 20% molar yield by these conditions, there is the total sugar accountability being greater than 90%.Deposit visible generation of not dissolving humin hardly.
For HFCS 90 syrup processed in identical device, the highest HMF yield and sugared accountability comprise an individual system, this system: sulphuric acid (wt 0.5% by sugar), the initial solid bulk concentration of 10% and Fast Heating (the wherein system back pressure of 1MPa gauge pressure (150 pounds/square inch) of reactant mixture injected by live (open) steam, the steam pressure of 1.4MPa gauge pressure (200 pounds/square inch), the time of under the reaction temperature provided 11 minutes is being provided by live (open) steam) and the quick cooling of this product mixtures before earth pressure release.This reaction controlling set point is 185 DEG C and is 179 DEG C at the maximum temperature that the end of stationary tube realizes.Obtain the HMF being up to 31% molar yield from HFCS 90 by these conditions, there is the total sugar accountability being greater than 95%.In addition there is visible generation of not dissolving humin hardly.
The quick cooling of this mixture 18 can be completed by various means.Such as, although at least use brazed-plate heat exchanger in some before depressurizing at following instance, the exchanger of other types can be used.Other options of personnel for the conventional technical ability in this area will be obvious.
To be appreciated that, this acid-catalyzed dehydration step 16 can according to one in batches, semi-batch or continuous print mode carry out.For containing hexose material dehydration to HMF, be previously described multiple acid catalyst, that comprise homogeneous phase with heterogeneous solid acid catalyst.Recycling is used in view of solid acid catalyst is more easily separated and reclaims, they will be preferred, but select in the presence of water a kind of and may be problematic by the catalyst maintaining gratifying activity and stability at the temperature for carrying out required by this dehydration 16.Sulphuric acid to be used in the example that WO 2013/106136 applies for and in following example, and provides good productive rate and excellent sugared accountability.
By following instance, the present invention is described:
example 1 and comparison example 1
Fructose (5g) is dissolved in 7mL water, and is loaded in two neck 25mL round-bottomed flask.This flask is equipped with a pipe to be equipped with reflux condenser with jet gas (or dry air (comparison example 1) or nitrogen (example 1)) through this solution.Spray this gas (dry air or nitrogen) and continue 5 minutes through this solution, then a concentrated sulphuric acid is added in this solution.Then close this flask with rubber septum, insert 16 metering syringe needles and allow jet gas escape and reflux 7 hours.After the response time of 7 hours, composition from both dry air injection and nitrogen jet test is amber, but there is no levulic acid and formic acid (table 1) from the composition of the proton N MR reactor of nitrogen jet test, but the dry air injection reactor composition of routine shows significant quantity both.
Table 1
example 2-5 and comparison example 2-5
Weighing scale 1000ppm (example 2) by butylated hydroxyanisol (BHA) to comprise 500mg melting in the bottle of Hydroxymethylfurfural.Vortex stirs this mixture, is then positioned in the baking oven being set as 85 DEG C.In order to compare, melt Hydroxymethylfurfural by comprising 500mg but not having the bottle of BHA (comparison example 2) to be positioned in the baking oven on this first bottle side.
Second group of example (example 3 and comparison example 3) by HMF and the 150mg of 850mg water is combined preparation, the BHA of interpolation 1000ppm equivalent in one of these samples, and to not substance in second.Two kinds of sample vigorous stirring are positioned in 85 DEG C of baking ovens.
Then by by HMF and the 900mg of 100mg water in conjunction with preparation four in water by weight 10% the sample of HMF.The BHA of 1000ppm equivalent is added in one of these samples (example 4).For the second sample (example 5), sealed to preserve this HMF under an argon through this solution purging air and this bottle by bubbling argon.For the 3rd sample (comparison example 4), the formic acid of the quality 10% by HMF is added in this bottle.Do not revise the 4th sample (comparison example 5) at all.After vigorous stirring, these four kinds of samples all are positioned in this baking oven of 85 DEG C again.
At 1 week and and then the component (except the sample that argon sprays) of the different bottle of post analysis at 2 weeks, result is accordingly shown in table 2 and 3:
Table 2-mono-week
Table 3-two weeks
example 6 and 7
Carry out these examples to evaluate this antioxidant BHA whether also by the stable ester except the HMF before HMF and ether derivant effectively.
ester derivant:for ester example, AcHMF (AcHMF) be (from aldrich company (Aldrich)) that be purchased and from normal hexane/MTBE mixtures recrystallize to improve its purity.To in the bottle comprising 500ppm equivalent BHA, add the AcHMF of 900mg.For comparing, preparation does not have second sample comprising the AcHMF of 700mg of BHA.Use this headroom of argon purge and melt and mix this AcHMF.These samples to be exposed in air atmosphere again and to be positioned in the baking oven of the dark of 85 DEG C, and after one week and again analyze after the two weeks.
This stabilizing agent does not clearly have detrimental effect, but at least under these conditions and in tested timetable, both makes these results under cited condition be uncertain without any significant degraded.
Table 4
By HMF and AcHMF using Ultra Performance Liquid Chromatography (UPLC) analysis of Waters Acquity H-Class UPLC device (having the TUV detector-monitor under 280nm) to be used for ester example, and describe following additional analysis in detail:
Post: Waters BEH C182.1 × 50mm, 1.7 m
Temperature: 50 DEG C
Flow velocity: 0.5mL/min
Purge solvent: 10% acetonitrile
Cleaning solvent: 50% acetonitrile
Solvent C: 50% acetonitrile
Solvent D: water
Gradient:
Volume injected: 0.5uL
Running time: 2.5min
ether derivant:for the ether derivant of HMF, from normal hexane, recrystallize 5-butoxymethyl furfural (BMF) is not until have Butyl acetylpropanoate can be observed by NMR.Being added in the bottle comprising 500ppm equivalent BHA by BMF (700mg) is then abundant mixing.In order to compare, the BMF of 300mg is positioned over and not comprise in the bottle of BHA.These bottles to be remained in the dark baking oven of 85 DEG C and sampling is used for analyzing after 1 and 2 weekly intervals.
These test results are as illustrated in table 5:
Table 5
By gas chromatographic analysis BMF.With acetonitrile, this diluted sample is measured GC area percentage, as reported in table 5 to the concentration of 1mg/mL.>99.9% by GC area parent material.Although and the catabolite of not all is differentiated and although some catabolites may not be detected really, these results demonstrate BHA and contribute to making this ether derivant BMF stabilisation even so.
The detail of analytical method is as follows:
Instrument: Agilent 7890 GC with 7693 automatic samplers
Post: m × 0.25, DB-5UI60m × 250 m
Carrier gas: H
2
Flow velocity: 1mL/min (constant)
Injection temperature: 200 DEG C
Shunting: 50:1
Detector: 340 DEG C
Temperature program(me): initial: 50 DEG C
Gradient 1:5 °/min to 180 DEG C
Gradient 2:20 °/min to 200 DEG C keeps 1min
Claims (9)
1., for manufacturing a method for Hydroxymethylfurfural from the aqueous solution comprising one or more hexoses, the method comprises makes this aqueous hexose solution be exposed to a kind of acid dewater by subtracting in one in oxygen environment.
2. method according to claim 1, a kind of ester wherein forming Hydroxymethylfurfural by carrying out accordingly dewatering under the existence of alcohol or carboxylic acid or ether derivant.
3. the method according to any one of claim 1 or 2, wherein by another kind of noble gas is ejected into carry out this dehydration reactor in replace oxygen from the headroom of this reactor.
4. method according to claim 3, comprises nitrogen or carbon dioxide jet in this reactor.
5., for improvement of a method for the degradation resistance of Hydroxymethylfurfural or Hydroxymethylfurfural derivant, the method comprises adds one or more antioxidants.
6. method according to claim 8, wherein butylated hydroxyanisol is comprised in these one or more antioxidants.
7. improve a Hydroxymethylfurfural compositions for stability, comprise Hydroxymethylfurfural and one or more antioxidants.
8. compositions according to claim 7, comprises Hydroxymethylfurfural and butylated hydroxyanisol.
9., for improvement of the method for Hydroxymethylfurfural degradation resistance before using stored, the method is included in one and subtracts in oxygen environment and store this Hydroxymethylfurfural.
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| US201361782539P | 2013-03-14 | 2013-03-14 | |
| US61/782,539 | 2013-03-14 | ||
| PCT/US2014/018186 WO2014158554A1 (en) | 2013-03-14 | 2014-02-25 | Process for making hmf from sugars with reduced byproduct formation, and improved stability hmf compositions |
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| CN112334453A (en) * | 2018-06-18 | 2021-02-05 | 阿彻丹尼尔斯米德兰德公司 | Color stabilization of monomers and other reactants for forming bio-based polymers |
| CN116178314A (en) * | 2021-11-29 | 2023-05-30 | 中国科学院宁波材料技术与工程研究所 | Method for improving storage and transportation stability of 5-hydroxymethylfurfural |
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| PL3401312T3 (en) * | 2017-05-08 | 2020-03-31 | Avalon Industries Ag | Method for stabilisation of hydroxymethylfurfural (hmf) |
| DE102018208510A1 (en) | 2018-05-29 | 2019-12-05 | Südzucker AG | Salt and acid mixture catalyzed HMF production |
| DE102018208507A1 (en) | 2018-05-29 | 2019-12-05 | Südzucker AG | Anolyte fraction-catalyzed HMF production |
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| RU2659166C2 (en) | 2018-06-28 |
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